CN104788344A - Bifunctional fluorescent probe adopting anthracene as matrix, as well as preparation method and application - Google Patents
Bifunctional fluorescent probe adopting anthracene as matrix, as well as preparation method and application Download PDFInfo
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 45
- 239000011159 matrix material Substances 0.000 title claims abstract description 14
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 9
- -1 iron ions Chemical class 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 11
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 150000002540 isothiocyanates Chemical class 0.000 claims description 4
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 claims description 4
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Chemical group 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 claims 1
- 239000011737 fluorine Substances 0.000 abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001917 fluorescence detection Methods 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract 2
- 238000005886 esterification reaction Methods 0.000 abstract 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 abstract 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 abstract 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract 1
- GRHBQAYDJPGGLF-UHFFFAOYSA-N isothiocyanic acid Chemical compound N=C=S GRHBQAYDJPGGLF-UHFFFAOYSA-N 0.000 abstract 1
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- NZCHHEFOTMKOJX-UHFFFAOYSA-K [6-[[3-carboxy-4-(3-oxido-6-oxoxanthen-9-yl)phenyl]carbamothioylamino]hexoxy-oxidophosphoryl] [5-(2,4-dioxopyrimidin-1-yl)-3,4-dihydroxyoxolan-2-yl]methyl phosphate Chemical compound O1C(COP([O-])(=O)OP([O-])(=O)OCCCCCCNC(=S)NC=2C=C(C(=CC=2)C2=C3C=CC(=O)C=C3OC3=CC([O-])=CC=C32)C(O)=O)C(O)C(O)C1N1C=CC(=O)NC1=O NZCHHEFOTMKOJX-UHFFFAOYSA-K 0.000 description 15
- 238000002189 fluorescence spectrum Methods 0.000 description 10
- 239000012085 test solution Substances 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000012921 fluorescence analysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 206010007027 Calculus urinary Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 208000006454 hepatitis Diseases 0.000 description 1
- 231100000283 hepatitis Toxicity 0.000 description 1
- 238000011246 intracellular protein detection Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000005014 resonance ionization mass spectroscopy Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- OFBPGACXRPVDQW-UHFFFAOYSA-N thiirane 1,1-dioxide Chemical compound O=S1(=O)CC1 OFBPGACXRPVDQW-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 208000008281 urolithiasis Diseases 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides a bifunctional fluorescent probe which is provided with the structure of the general formula I and adopts anthracene as the matrix. The preparation method of the bifunctional fluorescent probe comprises the following steps: conducting isocyanic acid esterification or isothiocyanic acid esterification on 9-anthracene methylamine; conducting the nucleophilic addition reaction to obtain the bifunctional fluorescent probe. The bifunctional fluorescent probe has the good fluorescence detection effect on iron ions; moreover, the system composed of the bifunctional fluorescent probe and the iron ions has the selective fluorescence enhanced detection effect on fluorine ions.
Description
Technical Field
The invention relates to a bifunctional fluorescent probe compound taking anthracene as a matrix, a preparation method and application thereof, and belongs to ion detection in the field of fine chemical engineering.
Background
Iron is one of the essential elements of human body, and its function is irreplaceable. It is a cofactor of biological enzymes and plays a crucial role in oxygen transmission and metabolism. If the content of the iron element is abnormal, a plurality of diseases can be caused, such as: gastrointestinal malignant tumor, hepatitis, senile dementia, etc. Therefore, the method has very important significance in detecting the content of iron in the living body. The traditional method for detecting the content of iron ions comprises an atomic absorption spectrometry, a resonance ionization mass spectrometry isotope dilution method, a chromatography method and the like. In recent years, fluorescence detection methods have attracted much attention from researchers because of their advantages such as high sensitivity and rapid response (chem.rev.2013,113, 192-270; anal.chim.acta.2014,812, 145-151).
Anions are ubiquitous in living bodies and play an important role, wherein fluoride ions are one of trace elements indispensable to human bodies. Fluorine is an important and essential component of bone and teeth. A proper amount of fluoride ions can effectively prevent the occurrence of dental caries diseases, so trace amount of fluoride ions are contained in the toothpaste. If a large amount of fluorine ions are taken, fluorosis may be caused, and then diseases such as osteoporosis, urolithiasis and the like are caused; the serious person may affect the mental and physiological systems of the child. Drinking water in daily life contains a trace amount of fluoride ions. The detection of fluoride ions is particularly important and critical. (chem.Rev.2014,114, 5511-5571; chem.Commun.2009, 2809-2829; chem.Soc.Rev.2010,39, 3746-3771).
The method for detecting the fluorinion comprises an electrochemical method,19F-NMR analysis, UV analysis, and fluorescence analysis. The first three methods all have certain limitations, such as: expensive equipment, inability to detect in real time, etc. In addition, fluorescence analysis has advantages such as high sensitivity, real-time detection, ultra-low concentration detection, and intracellular detection, and thus fluorescence detection has recently been favored by researchers.
At present, the detection of iron ions and fluorine ions by using the same fluorescent probe is only reported. Fluorescent probes based on pyrene, 6, 13-pentabenzoquinone, naphthalene, quinoline and benzimidazole can well realize the fluorescent detection of iron ions and fluorine ions (Tetrahedron Lett.2010,51, 5559-. Therefore, the research of the fluorescent probe based on the dual-function anthracene has certain innovation and value.
Disclosure of Invention
The invention aims to provide a bifunctional fluorescent probe which has excellent performance and takes anthracene as a matrix for detecting iron ions and fluoride ions. The bifunctional fluorescent probe taking anthracene as a matrix has a structure of a general formula I:
wherein X is an oxygen atom or a sulfur atom.
The invention also provides a preparation method of the dual-function fluorescent probe taking anthracene as a matrix, which comprises the following steps:
firstly, isocyanation or isothiocyanation: reacting 9-anthracenemethamine with triphosgene or thiophosgene to obtain an intermediate 9-anthracenemethyl isocyanate or 9-anthracenemethyl isothiocyanate;
and the addition reaction: reacting the intermediate 9-anthracene methyl isocyanate or 9-anthracene methyl isothiocyanate with an ammonia solution at the temperature of 0-40 ℃ for 1-48 hours to obtain a fluorescent probe; the ammonia solution is one of a methanol solution of ammonia, an ethanol solution of ammonia, a tetrahydrofuran solution of ammonia or a 1, 4-dioxane solution of ammonia.
In the steps of the method, the intermediate 9-anthracene methyl isocyanate is prepared by carrying out a conventional isocyanation reaction on 9-anthracene methyl amine and triphosgene.
In the steps of the method, the preparation method of the intermediate 9-anthracene methyl isothiocyanate comprises the steps of adding 9-anthracene methyl amine and thiophosgene into a mixed solvent of dichloromethane and water, adding deacidifying agent calcium carbonate, and reacting for 1-24 hours at 0-50 ℃. The mass ratio of the thiophosgene to the 9-anthracenemethamine is 1:1-2: 1; the mass ratio of the calcium carbonate to the 9-anthracenemethamine is 2:1-3: 1. The volume ratio of the dichloromethane to the water is 0.5:1-2: 1.
The preparation method of the bifunctional fluorescent probe with anthracene as a matrix comprises the following steps that in the second step, the ammonia solution is preferably tetrahydrofuran solution of ammonia, and the concentration of the ammonia solution is 0.2-2 mol/L.
In another aspect, the invention also provides the application of the fluorescent probe taking anthracene as a matrix in detection of iron ions and fluorine ions.
The fluorescent probe provided by the invention can rapidly, accurately, real-timely and selectively realize the fluorescent detection of iron ions in a mixed solvent of dimethyl sulfoxide and water; meanwhile, the system containing iron ions and the fluorescent probe can selectively realize the fluorescence enhancement detection of the fluorine ions.
Compared with the prior art, the invention has the advantages that:
(1) the fluorescent probe has relatively cheap raw materials and relatively simple synthesis steps;
(2) the fluorescence probe has good selectivity for ion detection, the operation of a fluorescence titration experiment is simple, and the fluorescence change is sharp; and the ion pair fluorescent probe has obvious color change under visible light, and is easy to observe by naked eyes.
Drawings
FIG. 1a shows a fluorescent probe 1 and Fe under visible light3+And F-A color change after the action; wherein,
no. 1 is a fluorescent probe 1; no. 2 is fluorescent probe 1 and Fe3+The function of (1); no. 3 is fluorescent probe 1-Fe3+Systems and F-The function of (1);
FIG. 1b shows fluorescent probes 1 and Fe under UV-365 nm3+And F-A color change after the action; wherein,
no. 1 is a fluorescent probe 1; no. 2 is fluorescent probe 1 and Fe3+The function of (1); no. 3 is fluorescent probe 1-Fe3+Systems and F-The function of (1);
FIG. 2 fluorescent Probe 1 with varying amounts of Fe3+Acting on a fluorescence spectrum;
FIG. 3 fluorescent Probe 2 with varying amounts of Fe3+Acting on a fluorescence spectrum;
FIG. 4 shows the fluorescence spectrum of the fluorescent probe 1 when it reacts with different metal ions;
FIG. 5 fluorescent Probe 1-Fe3+Systems with different amounts of F-Acting on a fluorescence spectrum;
FIG. 6 fluorescent Probe 2-Fe3+With different amounts of F-Acting on a fluorescence spectrum;
FIG. 7 fluorescent Probe 1-Fe3+Fluorescence spectrum of different anions.
Detailed Description
The present invention is described in detail with reference to the following examples, which are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept thereof within the technical scope of the present invention.
Example 1 preparation of fluorescent Probe 1
(1) Synthesis of 9-anthracenemethyl isocyanate
828mg of 9-anthracenemethamine is dissolved in 80mL of dichloromethane at room temperature, 8mL of dichloromethane solution containing 1.2g of triphosgene is added dropwise, and the mixture is stirred for 1 hour at room temperature; then 8mL of dichloromethane solution containing 808mg of triethylamine is added dropwise to react for 24 hours; saturated sodium bicarbonate was added thereto to adjust the pH to neutral, liquid separation was performed, the aqueous layer was extracted with dichloromethane, liquid separation was performed, the organic layer was washed with water, the organic layer was dried over magnesium sulfate, and rotary evaporation was performed to obtain 800mg of intermediate 9-anthracenemethylisocyanate with a yield of 85%.
1H-NMR(400MHz,CDCl3),8.51(s,1H),8.27(d,2H,J＝8.0Hz),8.06(d,2H,J＝8.0Hz),7.62(t,2H,J＝8.0Hz),7.52(t,2H,J＝8.0Hz),5.36(s,2H,CH2)；
HRMS:Calcd for[M-NCO]+,191.0861；Found,191.0852.
(2) Synthesis of fluorescent Probe 1
And (2) dissolving 800mg of the 9-anthracene methyl isocyanate obtained in the last step in 80mL of tetrahydrofuran solution of ammonia gas (0.7mol/L) to react for 24 hours at room temperature, performing suction filtration, washing a filter cake with a small amount of tetrahydrofuran, and drying the filter cake to obtain 800mg of the fluorescent probe 1 with the yield of 93%.
1H-NMR(400MHz,DMSO-d6),8.60(s,1H),8.43(d,2H,J＝8.0Hz),8.11(d,2H,J＝8.0Hz),7.56(m,4H),6.42(s,1H),5.42(br,2H),5.18(s,2H)；13C-NMR(100MHz,DMSO-d6),158.7,131.8,131.6,129.3,126.7,125.7,125.0,36.7；
HRMS:Calcd for[M+H]+,251.1184；Found,251.1176.
Example 2 preparation of fluorescent Probe 2
(1) Synthesis of 9-anthracenemethyl isothiocyanate
414mg of 9-anthracenemethamine were dissolved in 20mL of methylene chloride, followed by addition of 520mg of calcium carbonate and 20mL of water, and finally 322mg of thiophosgene, and reacted at room temperature for 12 hours. And adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, extracting with dichloromethane, separating, washing an organic layer with water, drying the organic layer with magnesium sulfate, and performing rotary evaporation to obtain 380mg of intermediate 9-anthracenemethyl isothiocyanate with the yield of 76%.
1H-NMR(400MHz,CDCl3),8.54(s,1H),8.24(d,2H,J＝8.0Hz),8.07(d,2H,J＝8.0Hz),7.64(t,2H,J＝8.0Hz),7.54(t,2H,J＝8.0Hz),5.60(s,2H).
(2) Synthesis of fluorescent Probe 2
260mg of 9-anthracene methyl isothiocyanate obtained in the last step is dissolved in 30mL of tetrahydrofuran solution of ammonia gas (0.7mol/L) to react for 48 hours at room temperature, the reaction solvent is removed by rotary evaporation, and then 160mg of fluorescent probe 2 is obtained by column chromatography separation with the yield of 58%.
1H-NMR(400MHz,DMSO-d6),8.65(s,1H),8.42(d,2H,J＝8.0Hz),8.14(d,2H,J＝8.0Hz),7.93(s,1H),7.60(m,4H),6.95(br,2H),5.57(s,2H)；13C-NMR(100MHz,DMSO-d6),182.6,131.0,130.0,128.9,127.6,126.5,125.3,124.4,40.5；
HRMS:Calcd for[M+H]+,267.0956；Found,267.0951.
Example 3 fluorescent Probe 1 and Fe under visible light and 365nm3+And F-Function of
Accurately weighing 25mg of fluorescent probe 1, dissolving in 10mL of dimethyl sulfoxide, and dissolving 1mL of the fluorescent probe in 99mL of mixed solution of dimethyl sulfoxide and water with the volume ratio of 1:1 to obtain the fluorescent probe with the concentration of 10-4mol/L of test solution 1. Accurately measuring 3mL of test solution 1 each time, sequentially putting the test solution 1 into 3 sample bottles of No. 1, No. 2 and No. 3, then respectively adding 30 mu L of dimethyl sulfoxide solution of ferric trichloride with the concentration of 0.01mol/L into the sample bottles of No. 2 and No. 3, finally adding the dimethyl sulfoxide solution of tetrabutylammonium fluoride with the concentration of 30 mu L with the concentration of 0.01mol/L into the sample bottle of No. 3, uniformly shaking the sample bottles of No. 1, No. 2 and No. 3, and obtaining a result shown in a figure 1a under visible light; the results shown in FIG. 1b were obtained at 365nm UV.
Example 4 Effect of the amount of iron ions on the fluorescence emission of fluorescent Probe 1
10mL of the solution of example 3 was taken at a concentration of 10-4The mol/L test solution 1 is dissolved in 90mL of mixed solution of dimethyl sulfoxide and water (the volume ratio of dimethylene sulfone to water is 4:5) to prepare a solution with the concentration of 10-5mol/L of test solution 2. 3mL of the test solution 2 was placed in a cuvette, and 0.1 equivalent, 1 equivalent, 10 equivalents, 30 equivalents, 50 equivalents, 100 equivalents, and 200 equivalents of a dimethyl sulfoxide solution of ferric chloride were added in this order, and the fluorescence emission spectrum was measured under the excitation of 370nm, to obtain the results shown in FIG. 2. It can be seen from the graph that the fluorescence emission intensity significantly decreases as the amount of iron ions increases.
The same method can obtain the result of the influence of the amount of iron ions on the fluorescence emission of the fluorescent probe 2, as shown in FIG. 3.
Example 5 Effect of different Metal ions on the fluorescence emission of fluorescent Probe 1
3mL of each solution was taken at a concentration of 10 in example 3-5Adding 100 equivalent Fe into the cuvette by mol/L test solution 23+、Ca2+、Cr3+、Cu2+、Fe2+、K+、Li+、Mg2+、Mn2+、Na+、Ni2+And Zn2+The fluorescence emission spectrum was measured under the excitation light of 370nm, and the results shown in FIG. 4 were obtained. As can be seen from the figure, the fluorescent probe 1 can selectively recognize iron ions well.
Example 6 amount of fluoride ion vs. fluorescent Probe 1-Fe3+Influence of the fluorescence emission of the system
3mL of each solution was taken at a concentration of 10 in example 3-5The mol/L of the test solution 2 was put into a cuvette, and 100 equivalents of a dimethylsulfoxide solution of ferric chloride was added, and then 1 equivalent, 5 equivalents, 10 equivalents, 20 equivalents, 50 equivalents, 100 equivalents, 101 equivalents, 102 equivalents, 200 equivalents and 300 equivalents of a dimethylsulfoxide solution of tetrabutylammonium fluoride were added in this order, and the fluorescence emission spectrum was measured, to obtain the results shown in FIG. 5. As can be seen from the figure, the fluorescence of the system increases significantly as the amount of fluoride ions increases.
The same method can obtain the quantity of the fluorinion to the fluorescent probe 2-Fe3+The results of the influence of the fluorescence emission of the system are shown in FIG. 6.
Example 7 fluorescent Probe with different anion pairs 1-Fe3+Influence of the fluorescence emission of the system
3mL of each solution was taken at a concentration of 10 in example 3-5Adding 100 equivalents of dimethyl sulfoxide solution of ferric trichloride into a cuvette for mol/L of test solution 2, and then sequentially adding 100 equivalents of F-、Br-、Cl-、H2PO4 -、HSO4 -、CH3COO-、CNS-、CO3 2-、HCOO-And I-The fluorescence emission spectrum was measured under the excitation light of 370nm, and the results shown in FIG. 7 were obtained. As can be seen from the figure, the system can selectively recognize fluoride ions.
Claims (7)
1. A bifunctional fluorescent probe taking anthracene as a matrix is characterized in that: has a structure shown in a general formula I,
wherein X is an oxygen atom or a sulfur atom.
2. The method for preparing the dual-function fluorescent probe taking anthracene as a matrix, which is characterized by comprising the following steps:
firstly, isocyanation or isothiocyanation: reacting 9-anthracenemethamine with triphosgene or thiophosgene to obtain an intermediate 9-anthracenemethyl isocyanate or 9-anthracenemethyl isothiocyanate;
and the addition reaction: reacting the intermediate 9-anthracene methyl isocyanate or 9-anthracene methyl isothiocyanate with an ammonia solution at the temperature of 0-40 ℃ for 1-48 hours to obtain a fluorescent probe; the ammonia solution is one of methanol, ethanol, tetrahydrofuran or 1, 4-dioxane solution of ammonia.
3. The method for preparing the dual-function fluorescent probe taking anthracene as a parent body according to claim 2, is characterized in that the method for preparing 9-anthracene methyl isothiocyanate in the step of preparing comprises the following steps: adding 9-anthracenemethamine and thiophosgene into a mixed solvent of dichloromethane and water, adding acid-binding agent calcium carbonate, and reacting at 0-50 ℃ for 1-24 hours.
4. The method for preparing the dual-functional fluorescent probe taking anthracene as a matrix according to claim 3, wherein the method comprises the following steps: the mass ratio of the thiophosgene to the 9-anthracene methylamine is 1:1-2: 1; the mass ratio of calcium carbonate to 9-anthracenemethamine is 2:1-3: 1.
5. The method for preparing the dual-functional fluorescent probe taking anthracene as a matrix according to claim 3, wherein the method comprises the following steps: the volume ratio of the dichloromethane to the water is 0.5:1-2: 1.
6. The method for preparing the dual-functional fluorescent probe taking anthracene as a matrix according to claim 2, wherein the method comprises the following steps: in the step II, the ammonia solution is tetrahydrofuran solution of ammonia with the concentration of 0.2-2 mol/L.
7. The use of the anthracene-based fluorescent probe of claim 1 for the detection of iron and fluoride ions.
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| JP2018516886A (en) * | 2015-09-02 | 2018-06-28 | 大連理工大学 | Carboxylic ion cross-linked dinuclear iron sulfur cluster fluorescent probe, its production method and its use |
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